PT97366A - METHOD FOR PREPARING A CETONE AND / OR ALCOHOL - Google Patents

Description

72 407 6662 EN D ..... E ..... S ..... C ..... R ..... I ..... Ç ..... Ã ... .0.

The invention relates to a process for preparing a ketone and / or alcohol by oxidation of a cyclic hydrocarbon having at least 13 carbon atoms with oxygen to form a hydroperoxide followed by a decomposition of the hydroperoxide formed, in the presence of an organic complex of metal -

In Liebigs Ann-Chem. 757: pp. 109-120 (1972) Kropf and Knaa-ck describe an investigation of the auto-oxidation of phenylcycloheptane (a cyclic hydrocarbon with 13 C atoms) with a Cu-phthalocyanine as a catalyst to form the corresponding peroxide. Some mention is made of the formation of a cyclic ketone, but the publication is substantially directed to the formation of the hydroperoxide. There is no information regarding the selectivity of the reaction-

DE-A-1 940 -051 discloses a process for oxidizing aromatic hydrocarbons with ring condensate systems, such as anthracene or fluorene, to form the corresponding oxidation product (such as anthraquinone). In that process, the catalyst used is a salt of a heavy metal- No mention is made of the targeting formation of the intermediate hydroperoxide-

It has been found that for the selective preparation of a ketone and / or alcohol by the oxidation of a cyclic hydrocarbon having at least 13 C atoms, a better result is obtained if the formation of the hydroperoxide and its decomposition are carried out as separate steps of the Therefore, an optimum preparation of the hydroperoxide may be coupled with an optimum conversion thereof to the corresponding ketone and /

To the extent that an organic metal complex is applied in the processes described in the literature, the complex is used in a soluble form, i.e. the complex is present in the oxidizing liquid in a homogeneously dissolved state. As a consequence, the complex must necessarily be separated from the reaction mixture separately, for example by distillation. In addition to the fact that,

Since such a thermal effect, (a part of) thermally sensitive complex can be lost, the complex must also be recovered from the distillation product before being used again in the process.

Thus, there is a need for a process in which the above and other disadvantages of known processes are overcome. This is done according to the invention by the decomposition of the hydroperoxide being carried out in the presence of a metal complex of immobilized porphyrin and / or phthalocyanine on a vehicle.

Due to immobilization on the vehicle, a catalyst is obtained which can be readily separated from the reaction phase and which combines surprisingly good, maintained and stable activity with a good selectivity towards the ketone and / or the alcohol - the starting material which may be used for the process according to the invention may be any substituted or unsubstituted cyclic hydrocarbon having at least 13 carbon atoms. The oxidation of such a compound is such that the hydroperoxide is formed on a secondary carbon atom of a hydrocarbon which has secondary and possibly primary carbon atoms. The hydroperoxide is formed on a tertiary carbon atom if (in addition to any secondary and primary carbon atoms) that atom is present in the compound to be oxidized. In the case of a secondary hydroperoxide, this hydroperoxide is converted during the composition to form a ketone and / or an alcohol; in the case of a tertiary hydroperoxide conversion into an alcohol takes place.

In Beilstein (V-Hauptwerk) many cyclic hydrocarbons are suitable for the invention. In addition to the following non-limiting list, reference may be made thereto.

Cyclic hydrocarbons which may, according to one process of the invention, be converted to a ketone and / or alcohol have at least 13 carbon atoms. Preferably they have 13-40 carbon atoms, in particular 13-30. Examples of 4-

(A) a direct bond or (CH2) n &lt; A &gt; R 2 is hydrogen, methyl, ethyl, R 2, R 2, isopropyl, isobutyl, tert-butyl, etc., aryl; B. R3 / nR-methylene, cycloalkylene; R1 = hydrogen, methyl, ethyl, <iso -propyl, isobutyl, tert-butyl, etc., aryl; R1 is R3: = cycloalkyl, methyl, hydrogen;

R1, R2-hydrogen, methyl, ethyl, isopropyl, isobutyl, tert-butyl, etc., aryl; R 3 is a direct bond or (CH 2) n n = 1, 2 R 4 is a direct bond or (C 1 -U) n m = 1, 2; R 2 = hydrogen, methyl, ethyl, ethyl, isopropyl, isobutyl, tert-butyl, aryl, etc. R 2 = hydrogen, methyl, isopropyl, isobutyl, tert-butyl , aryl, etc .;

72 407 6662 PT &lt; 2 &gt;

Methylene, cycloalkyl, R 1 and / or R 2 may represent one or more substituents on the ring,

Examples of such compounds are:

For group A:

For group B:

For the C-group: diphenylmethane diphenylethane 2-ethyl-1, β-biphenyl 3-ethyl-1 H -1-biphenyl 2-isopropyl-1 H -benphenyl phenylcyclododecane phenylcycloheptane 2-methyl-1-cyclo cycloheptyl-benzene 2-isopropylnaphthalene 1-isobutylnaphthalene 2-isobutylnaphthalene-1-ethyl-4-methylnaphthalene

For group D:

For the group E: For the group F: -fluorene-9-methylfluorene-9,10-dihydrophenanthrene-1-methylfluorene-1,8-dimethylfluorene-1S-tetrahydro-6-phenylnaphthalene -1,2-dicyclohexyl-ethane-1,1-dicyclohexyl methane

The metal complexes of phthalocyanine and porphyrin which may be used in a process according to the invention are known per se. With respect to this reference can be made, for example, to the article by J. Manassen in Cat. Rev. Sci. Eng., 9 (2), 223--43 (1974). The preparation of such complexes is described, tert. alia, by B. Berezin in Coordination Compounds of Porphyrins and Phtalocyanines, Wiley N.Y. 1981. The starting material for the

The compound formulas of these compounds are as follows: A compound of the formula: ## STR5 ## wherein R 1, R 2, R 3,

11 10

Phthalocyanine Porphyrin

The phthalocyanines can be substituted at the positions 1-16 indicated above at the positions 1- *, 6 * 9 * 11 * 14, 16, and 19. The substituents used may be: alkyl groups, whether or not they are substituted or functionalized,

alkenyl groups, whether or not substituted or functionalized, are unsubstituted or functionalized phenyl groups, amines, sulphonic acids, carboxylic acids, aldehydes and their derivatives. The complexation of a porphyrin can for example be effected by the introduction of porphyrin in DMF (dimethylformamide) and addition, under reflux, of the metal to be incorporated as metal chloride. Phthalocyanines can be synthesized starting from molecular fragments such as phthalonitrile, phthalimide and phthalic anhydride. The metal sources used may be metal chlorides. In some cases, urea is used as a donor of nitrogen and ammonium molybdate as a catalyst.

The most suitable metals to apply the process are Co, Mn,

72 407 6662 EN -7

Cr, Fe and / or V, but in principle any transition metal capable of forming organometallic complexes with said products will be suitable.

Mixtures of said metals may also be used.

According to the invention, the organometallic complexes are attached to (immobilized on) a carrier. The carrier can be any material which can be used to effect a bond with the complex. In this respect, a coordinating ionogenic bond can be considered as well as In order to obtain an effective bond, the substituted groups of the organometallic complexes must be such as to make such bonding possible. This can be obtained for example by using complexes containing one or more amino acid or carboxylic acid groups or combinations of the same"

The carrier to be used may be of an inorganic nature as well as an organic polymer. The carrier must also be provided with one or more groups capable of immobilising the or ganometallic complex. Among the requirements which the vehicle must satisfy is that of the carrier must have sufficient reactive groups to enable it to achieve an acceptable degree of loading. Suitable reactive groups are for example COOH, NHR * OH * SGgH, Cl * Br * I, but also phenyl and associated groups- In addition * the material should not dissolve in one of the components present in the process stream * it must be inert to the reactions that occur and it must be mechanically stable -

Inorganic carriers * such as alumina, TiO 2 * SiO 2 or organic vehicles * such as polystyrene * ethylene-vinyl acetate copolymer * acid-modified polyethylene or anhydride are suitable as carriers *.

When, for example, silica is used as the carrier material, the coupling may be effected, for example by starting from a phthalo-cyanine or porphyrin with one or more halogen-containing substituents (compounds). The starting material is heated for some -8-

6662 time in pyridine together with silica. The solid is subsequently filtered, washed and dried.

When, for example, polystyrene is used as the carrier material, the bond may be effected for example by starting from a phthalocyanine or porphyrin with one or more COOH-containing substituents. By application of a Friedel-Crafts reaction it can be bound to polystyrene '

In the process according to the invention the oxidation of the cyclic hydrocarbide in the liquid phase is carried out with for example pure oxygen or a mixture of oxygen and inert gas at a temperature of 70-200 ° C for 1 / 2-24 hours In the 1-30% process, for example * the hydrocarbon is converted so as to obtain a maximum yield of intermediate hydroperoxide. The pressure in this oxidation process is not critical and is * for practical reasons * generally between 100 kPa and 5000 kPa (1 and 50 bar). The reaction can be carried out in the cyclic hydrocarbon as such, as well as by the application of a solvent The solvent used may be, for example, benzene or toluene. The oxidation of the cyclic hydrocarbon is preferably carried out in the absence of substances which promote the decomposition of the formed hydroperoxide, such as transition metal compounds, and for this reason preference is given in this oxidation process to the use of a reactor with an inert inner wall , for example an inner wall of passivated steel, aluminum, glass, enamel and the like. If the use of an oxidizing catalyst is further desired, the amount of transition metal should preferably be very small, for example of the order of 1-10 parts by weight * per million. The oxidizing catalyst used may consist of compounds of, for example, cobalt, chromium, manganese, iron, nickel, copper or mixtures thereof. The organometallic complexes described are also suitable. The decomposition of the hydroperoxide in the oxidation mixture is effected by means of the metal complexes immobilized on the basis of phthalocyanine and / or porphyrin. The decomposition catalyst may

72 407 6662 EN -9

be used in various ways - As applied on a vehicle 'sludge reactors can be used as well as, for example, filling beds to effect conversion of the hydroperoxide. The reaction heat released in the decomposition should be suitably collected and withdrawn to ensure proper control of the process temperature. This can be done very well, particularly when sludge reactors are used. During decomposition the desired temperature can be caused by for example, to be maintained by refluxing at least a portion of the heat to be withdrawn. No recirculation of the evaporated products which has a somewhat favorable effect on the yield of the desired product will be required. The amount of complex to be used is, for example, 1-250 ppm of metal, calculated relative to the oxidation mixture. Preference is given to the use of 5-150 ppm of metal. The temperature during decomposition is generally within the range The pressure chosen in the decomposition is usually slightly lower than in the oxidation. The decomposition is preferably carried out in the presence of oxygen. This causes the yield of the ketone and / or alcohol to be improved- time The residence time required for the reaction mixture can be readily determined by analysis of any non-decomposed peroxide. Typically a residence time between 5 and 300 minutes will be adequate, preferably the residence time will be chosen between 10-120 minutes-

Prior to the decomposition of the hydroperoxide in the oxidation mixture, the oxidation mixture may be treated, if desired, with water or with an aqueous alkali metal hydroxide or alkali metal carbonate solution for the removal and / or neutralization of the acids formed in the oxidation, for example at a pH of the aqueous phase of unconverted cyclic hydrocarbon, may be removed from the oxidation mixture for example by applying a distillation or flash evaporation process. The reaction mixture obtained on the decomposition of the hydroperoxide

with water if so desired to a distillation treatment while recovering the cyclic hydrocarbon which is to be returned and the ketone and / or alcohol. The invention will be further elucidated by the following examples.

Example IA 35 ml of DMF (dimethylformamide) was added 5 mmol of dicyclohexylcarbodiimide at room temperature. Subsequently, 0.4 mmol of co-tetrasulfonic acid phthalo-cyanine was added. This mixture was stirred for one hour at room temperature. 1 g of silica modified with 3-aminopropyltrimethoxysilane (BEI surface = 390 m2 / g, particle size 0.5-1 mm, N (nitrogen content) = 2.4% (weight), C (carbon content) = 6.5% (weight)) This mixture was stirred for 24 hours at room temperature, filtered and washed with ethanol and dichloromethane and dried at 60 ° C. The cobalt content was 0.56% (Weight)"

Example I was repeated with Fe and V-tetrasulfonic acid phthalocyanine as compounds to be bound. The metal content of the products was respectively 0.38% (by weight) of iron and 0.42% ( by weight of vanadium.

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In 200 ml of DMSO (dimethylsulfoxide) 2.0 g of Ti-tetraaminephthalocyanine were dissolved. To this solution was added 0.5 g of 2- (4-chlorosulphonylphenyl) ethyltrimethoxysilane modified silica (BET = 540 m S (sulfur content) ~ 4.3% (by weight)).

After stirring for one day, the loaded silica was filtered and washed with DMSO and acetone. The weight percent of titanium to silica was 0.37%.

In another preferred embodiment,

Example III was repeated with Fe and Co-tetraamphamophthalocyanine as compounds to be bound. The iron and cobalt contents were respectively 0.36 and 0.25% (by weight ) -

A solution of cobalt-tetrabromophthalocyanine in pyridine was added 10 grams of silica (particles having a diameter of 3 mm and a BET surface of approximately 60 m2 / gram). The suspension was stirred for 6 hours at After cooling, the suspension was filtered and washed with methanol and chloroform and dried. The reaction product was analyzed for its metal content (0.05% (w / w)) -

Example V was repeated with Co-monochlorophthalocyanine (metal content 0.08% (w / w) with the compound to be bound-

EXAMPLE V was repeated with (4- (3-bromo-1-propoxy) phenyl) -10,15,20-tritolylporphyrin as the compound to be ligated. , Cr, Co, V, Mn and Fe were incorporated as metals using the OMF method. All these products were analyzed for their metal content Results:

Cr: 0.09% (by weight) Mn: 0.06% (by weight)

Co: 0.05% (by weight) Fe: 0.06% (by weight) V: 0.04% (by weight)

20 grams of an oxidation mixture of a fluorene, containing 3% (by weight) of 9-hydroperoxyfluorene, 1% (by weight) of fluoro-nol and 1% (by weight) of fluorenone in fluorene dissolved in 200 grams of benzene was added such an amount of the catalyst mentioned in example I that the resulting metal concentration was 50 ppm. At a temperature of 65 ° C, the peroxide decomposed completely in 60 minutes. The rate constant k (based on a first-order decomposition) was 0.09

12 -

min ~ · * ·. The selectivity for fluorenol and fluorenone was 98.5%. The converted value (defined as moles of peroxide converted per mole of metal) that can be achieved in re-use was higher than 3500.

Comparative Experiment Example VIII was repeated with Co-phthalocyanine as catalyst. The catalyst was partially dissolved in the oxidation mixture. The reaction mixture was refluxed for 0.01 min. lower than 500.

Comparative experiment ..... Example VIII was repeated with Co-acetate as the catalyst. 0 k was 0.02 min &quot; 1. The catalyst, however, precipitated from the reaction mixture and could not be used again. The selectivity was 95%.

Example 7 To 20 grams of a trephenylmethane oxidation mixture containing 7 wt.% Triphenylmethanehydroperoxide and 2 wt.% Triphenylmethanol in triphenolmethane, dissolved in 200 grams of benzene, was added a solution of such an amount of the Fe catalyst mentioned in example II that the resulting metal concentration was 60 ppm. At a temperature of 65 ° C the peroxide was completely formed in 60 min. 0 k was 0.15 min -1, the selectivity to triphenylmethanol was 94.5%. The converted value that could be achieved in re-use was higher than 2200.

Example IX was repeated with the Fe catalyst of example IV. 0 k was 0.16 min-1 and the selectivity to triphenylmethanol was 94.5%.

72 407 6662 EN

Example IX was repeated with the Cr catalyst of example VII-0 K being 0.04 min &quot; -1 ' and the selectivity to triphenyl-methanol was 96.4%

To 20 ml of thionyl chloride were added 4 mmol of Co-tetracarboxyphthalocyanine. This mixture was stirred at room temperature for a few hours under N2. Subsequently, a suspension of 1,1,2- 2-tetrachloroethane and polystyrene (20 grams, 3% by weight of vinylbenzene, 22/50 mesh, macroporous 8000 nm). The reaction mixture was heated to 135 ° C and excess of 300 ° C was distilled off. Mass of the reactor was cooled to 12 ° C, after which 6 grams of AlCl 3 were added thereto. After that the solid was filtered, washed with 1,1,2,2-tetrachloroethane, methanol, basic water and HCl. The resulting solid was dried at 0 DEG C. The product was analyzed for the metal content (the cobalt content was 0.43% (by weight)) -

Example XIII was repeated with Mn-octacarboxyphthalocyanine as the compound to be coupled (the manganese content was 0.53% (w / w)) - S.X.® Plo ..... XIV. Example IX was repeated with 5,10,15,20-tetra (4-carboxyphenyl) porphyrin as the compound to be attached. The metals incorporated after the DMF method were Cr, Co, Mn, Cu and Fe-

All these products were analyzed for their metal-

Metal content;

Cr = 1.9% (by weight) Mn to 0.61% (by weight)

Co to 0.49% (by weight) Cu ~ 0.50% (by weight)

Fe = 0.64% (by weight)

72 407 6662

To a 17% (by weight) oxidation mixture of 2-isopropyl-hydroperoxy naphthalene containing 2-isopropylnaphthalene was added such an amount of said Co catalyst in example XII that the resulting metal concentration was 100 ppm peroxide completely decomposed in 60 minutes at a temperature of 85 DEG C. The rate constant k was 0.04 min 1- Selectivity over 2- isopropylhydroxynaphthalene was 96.2%. The converted value that can be achieved in re-use was higher than 2800-

Example XVI Example XV was repeated with the Mn catalyst of example XIII-0k was 0.003 min. The selectivity was 92.5%

Example ..... XVII

To a 2-ethyl-7-methylnaphthalene oxidation mixture containing 5% (by weight) of 2-ethyl (1-hydroxyperoxy) -7-methylnaphthalene, 1.5% (by weight) of 2-ethyl 9-hydroxy-7-methylnaphthalene and 0.8% (by weight) of 2-ethyl (1-aona) -7-methylnaphthalene in 2-ethyl-7-methylnaphthalene was added such an amount of the Cr catalyst mentioned in Example XIV so that the resulting concentration of metal was 85 ppm peroxide was completely decomposed in 60 minutes at a temperature of 95 DEG -04 DEG C. The selectivity towards alcohol and to the ketone was 98.2%. The catalyst could be re-used a large number of times-

Example ..... XVII.I. Example XVII was repeated with the Fe catalyst of Example XIV-0K in the range of 0.12 min. The alcohol and ketone selectivity was 105%

72 407 · * 6662

Exímio ..... XIX. Example XVIII was repeated, and air was also passed through the solution. As a result, selectivity to alcohol and ketone rose to 105%.

Example XVII was repeated with ditertiary butyl chromate as catalyst-0 .mu.m was 0.03 min.  € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ- Selectivity was 96.5%. After the experiment, it was found that the catalyst was deactivated; it was found that the newly added peroxide was not capable of being decomposed,

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Claims (7)

A process for the preparation of a ketone and / or an alcohol by oxidation of a cyclic hydrocarbon having at least 13 C atoms with oxygen to form a hydroperoxide followed by a decomposition in the presence of an organic complex of the hydroperoxide formed, characterized in that the decomposition is carried out in the presence of a metal complex of porphyrin or phthalocyanine immobilized on a carrier J Process according to claim 1, characterized in that the metal in the complex is Co, Mn, Cr, Fe and / or V ' A process according to any one of claims 1-2, characterized in that the carrier is inorganic in nature. A process according to any one of claims 1-2, characterized in that the carrier is of an organic polymeric nature A process according to any one of claims 1-4, characterized in that the preparation is carried out in a slurry reactor A process according to any one of claims 1-5, characterized in that 10-150 ppm of metal complex, calculated based on the metal, the complex and the oxidation mixture are applied. Process according to any one of claims 1-6, characterized in that the decomposition of the hydroperoxide is carried out in the presence of oxygen, Lisbon, &gt; 2. m By STAMICARBON B »V»